CN101296954A - Process for the manufacture of fluoroelastomers having bromine or iodine atom cure sites - Google Patents
Process for the manufacture of fluoroelastomers having bromine or iodine atom cure sites Download PDFInfo
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- CN101296954A CN101296954A CNA2006800402959A CN200680040295A CN101296954A CN 101296954 A CN101296954 A CN 101296954A CN A2006800402959 A CNA2006800402959 A CN A2006800402959A CN 200680040295 A CN200680040295 A CN 200680040295A CN 101296954 A CN101296954 A CN 101296954A
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Abstract
Fluoroelastomers having bromine, iodine or both iodine and bromine cure sites are prepared by an emulsion polymerization process wherein any iodine or bromine containing comonomers and any iodine or bromine containing chain transfer agents are introduced to the reactor as aqueous emulsions, optionally containing a surfactant.
Description
Technical field
The present invention relates to the method for fluoroelastomer that a kind of manufacturing has the cure sites of bromine, iodine or bromine and iodine atom, wherein will comprise the comonomer of described bromine or iodine atom or chain-transfer agent and add to polymerization reactor with the form of aqueous emulsion.
Background technology
Have excellent thermotolerance, oil-proofness and chemical-resistant fluoroelastomer and be widely used in sealing material, container and flexible pipe.The example of fluoroelastomer comprises and contains vinylidene fluoride (VF
2) multipolymer of unit and at least a other fluorine-containing monomer units, described other fluorochemical monomers for example R 1216 (HFP), tetrafluoroethylene (TFE), trifluorochloroethylene (CTFE), vinyl fluoride (VF) and fluoroether for example perfluor (alkyl vinyl ether) is (PAVE).The specific examples of PAVE comprise perfluor (methylvinylether) (PMVE), perfluor (ethyl vinyl ether) and perfluor (propyl vinyl ether).Other examples of fluoroelastomer comprise for example multipolymer of perfluor (methylvinylether) of tetrafluoroethylene and perfluor (alkyl vinyl ether).Ethene (E) and propylene (P) are for being generally used for preparing the non-fluorinated monomer of fluoroelastomer.
Use required physicals in order to develop most of end-uses, must fluoroelastomer is crosslinked.The preferred consolidation system that is used for many end-uses is the combination of organo-peroxide and polyfunctional unsaturated coagent.Coagent by with the fluorine-containing elastomer polymer chain backbone on cure sites reaction, form crosslinked.Preferred cure sites is the bromine or iodine atom that links to each other with carbon atom on the fluoroelastomer chain.
Usually prepare fluoroelastomer by free-radical emulsion polymerization.A kind of method of introducing iodine or bromine cure sites in fluoroelastomer is for carrying out polymerization in the presence of the chain-transfer agent that comprises iodine or bromine.Adopt this mode, iodine or bromine atoms link to each other with one or more ends of resulting fluoroelastomer.This chain-transfer agent has structure RX usually
n, wherein R can be C
1-C
3Hydrocarbon, C
1-C
6Fluorohydrocarbon, C
1-C
6Chlorofluorocarbons (CFCs) or C
2-C
8Perfluoroparaffin, X are iodine or bromine, and n=1 or 2 (United States Patent (USP) 4,243,770 and 4,973,633).
On the fluorine-containing elastomer polymer chain, introduce the another kind of common method of iodine or bromine cure sites for will contain iodine or bromated fluoroolefins or fluorovinyl ether cure site monomer and other monomers (for example VF2, HFP, TFE, PAVE, P, E etc.) copolymerization on a small quantity.Adopt this mode, cure sites can be along resulting polymer chain random distribution.
The general problem that use contains iodine or brominated cure sites or comonomer is usually the proportion height of these compounds.For example under 25 ℃, methylene iodide (CH
2I
2) proportion be 3.33, methylene bromide (CH
2Br
2) proportion be 2.51,1, the proportion of 4-diiodo-Octafluorobutane is 2.48,1, the proportion of 6-diiodo-ten difluoro hexanes is 2.35.When this high specific gravity material was added to polymerization reactor, free settling was in the bottom of reactor.Because these materials fall to reactor bottom, therefore introduce polymer chain unevenly, make a part of chain have unusual high-load cure sites, and other parts have the cure sites of unusual low levels.Can cause like this becoming undesirable by the product end-use performance of fluoroelastomer preparation.Hyperbaric another consequence is that a part contains iodine or bromine-containing compound even can not introduce in the polymkeric substance, the utilization ratio that causes containing iodine or bromine-containing compound reduces, and need that other waste reduction and disposal equipment captures any remnants contain iodine or brominated cure site monomer or chain-transfer agent.Owing to contain iodine or brominated chain-transfer agent can not be introduced polymer chain equably, therefore hyperbaric another consequence is resulting fluorine-containing elastomer polymer viscosity controller is poor.
Using many another problems that contain iodine or brominated cure site monomer or chain-transfer agent is solvability variation in water.This low-solubility will cause introducing these compounds change (J.Appl.Polym.Sci.51,21 (1994)) in emulsion polymerization repeatedly.In order in polymkeric substance, to introduce poorly soluble chain-transfer agent fully, need to reduce total polymerization speed, cause polymerization reactor efficient low like this.
In order to solve the problem of high specific gravity and low water-soluble, proposed to contain iodine or brominated cure site monomer or chain-transfer agent and be dissolved in the organic solvent, subsequently with this injection of solution to polymerization reactor (United States Patent (USP) 4,973,633 and 5,284,920).But, desolvate owing to need other waste reduction and disposal equipment from polymkeric substance or waste water, to remove, so this method is unsatisfactory.In addition, be difficult to find and do not influence and the gratifying solvent of the polyreaction that slows down.
The another kind of solution that proposes contains iodine chain-transfer agent (United States Patent (USP) 5,585,449) for introducing in the microemulsion to fluoridizing of spontaneous generation.But the shortcoming of this method is that the fluorinated oil that comprises microemulsion is retained in the polymkeric substance.These fluorinated oils can be detected (for example by GC with Headspace-MS), and can be influenced unfriendly with the bonding and abrasive properties and the food of metal and contact situation.
Summary of the invention
On the one hand, the invention provides a kind of method of making fluoroelastomer, described method comprises using and contains iodine or brominated chain-transfer agent and/or contain iodine or the emulsion of the machinery of brominated cure site monomer generation, wherein the average droplet size of gained emulsion is less than 50 μ m, and do not contain any organic solvent or oil substantially, and can choose wantonly and comprise tensio-active agent.
On the other hand, the invention provides the method that a kind of preparation has the fluoroelastomer of bromine, iodine or bromine and iodine cure sites.Described method comprises:
(A) in reactor, add a certain amount of aqueous solution;
(B) add a certain amount of initial monomeric mixture to form reaction medium in described reactor, described initial monomeric mixture comprises: i) first monomer, and described first monomer is selected from vinylidene fluoride and tetrafluoroethylene; But the ii) monomer of one or more other copolymerization different with described first monomer, wherein said other monomer is selected from Fluorine containing olefine, fluorine-containing ether, propylene, ethene and composition thereof;
(C) add at least a aqueous emulsion that comprises the solidified portion potential source in described reactor, described solidified portion potential source is selected from: i) contain the iodine cure site monomer, ii) brominated cure site monomer, iii) contain iodine chain-transfer agent and iv) brominated chain-transfer agent; The drop size of wherein said emulsion is less than 50 μ m; With
(D) the described monomer of polymerization in the presence of radical initiator has the fluoroelastomer of cure sites with formation.
Detailed Description Of The Invention
The present invention relates to be used to make the emulsion polymerization of the fluoroelastomer that comprises bromine, iodine or bromine and iodine atom cure sites.
Fluoroelastomer by method preparation of the present invention comprises the first monomeric copolymerization units other monomeric copolymerization units different with described first monomer with one or more, and described first monomer can be vinylidene fluoride (VF
2) or tetrafluoroethylene (TFE), described other monomer is selected from Fluorine containing olefine, fluorine-containing ether, propylene, ethene and composition thereof.Be present in content by the first monomeric copolymerization units in the fluoroelastomer of method of the present invention preparation and be not more than 85% of all comonomer total mole numbers of introducing fluoroelastomer.
Can comprise vinylidene fluoride, R 1216 (HFP), tetrafluoroethylene (TFE), 1,2,3,3,3-five fluorine propylene (1-HPFP), trifluorochloroethylene (CTFE) and vinyl fluoride with the example hydrocarbon of the Fluorine containing olefine of first monomer copolymerization.
The example that can be used for fluorine-containing ether of the present invention comprises perfluor (alkyl vinyl ether), perfluor (alkyl alkene ether) and perfluor (alkoxyl group alkene ether).
Be suitable as monomeric perfluor (alkyl vinyl ether) and (PAVE) comprise the material of following formula
CF
2＝CFO(R
f′O)
n(R
f″O)
mR
f (I)
R wherein
F 'And R
F "For having the different straight or branched perfluorinated alkylidene of 2-6 carbon atom, m and n independently are 0-10, R
fFor having the perfluoroalkyl of 1-6 carbon atom.
A preferred class perfluor (alkyl vinyl ether) comprises the composition of following formula
CF
2＝CFO(CF
2CFXO)
nR
f (II)
Wherein X is F or CF
3, n is 0-5, R
fFor having the perfluoroalkyl of 1-6 carbon atom.
A most preferred class perfluor (alkyl vinyl ether) comprises that wherein n is 0 or 1 and R
fThe ether that comprises 1-3 carbon atom.The example of this perfluorinated ethers comprise perfluor (methylvinylether) (PMVE) and perfluor (propyl vinyl ether) (PPVE).Other available monomers comprise the compound of following formula
CF
2＝CFO[(CF
2)
mCF
2CFZO]
nR
f (III)
R wherein
fFor having the perfluoroalkyl of 1-6 carbon atom, m=0 or 1, n=0-5, and Z=F or CF
3
Preferred material comprises wherein R in this type of
fBe C
3F
7, m=0, and the compound of n=1.
Other perfluor (alkyl vinyl ether) monomer comprises the compound of following formula
CF
2＝CFO[(CF
2CF{CF
3}O)
n(CF
2CF
2CF
2O)
m(CF
2)p]C
xF
2x+1 (IV)
Wherein m and n independence=0-10, p=0-3, and x=1-5.
Preferred material comprises wherein n=0-1, m=0-1, and the compound of x=1 in this type of.
Other examples of available perfluor (alkyl vinyl ether) comprise
CF
2＝CFOCF
2CF(CF
3)O(CF
2O)
mC
nF
2n+1 (V)
N=1-5 wherein, m=1-3, and wherein preferred n=1.
Be suitable for use as the material that monomeric perfluor (alkyl alkene ether) comprises following formula VI
R
fO(CF
2)
nCF＝CF
2 (VI)
R wherein
fFor comprising 1-20, preferred 1-10, the perfluorination straight or branched aliphatic group of 1-4 carbon atom most preferably, and n is the integer of 1-4.Specific examples comprises perfluor (propoxy-allyl ethers) and perfluor (propoxy-butenyl ether).
The different R that are among the formula VI of perfluor (alkoxyl group alkene ether) and perfluor (alkyl alkene ether)
fIn aliphatic chain, comprise at least one Sauerstoffatom.Specific examples is including, but not limited to perfluor (methoxy ethoxy allyl ethers).
If the copolymerization units of fluorine-containing ether is present in the fluoroelastomer of the present invention, then ether unit content is generally the 25-75% of described fluoroelastomer gross weight.If use perfluor (methyl ethylene) ether, then preferred fluoroelastomer comprises the PMVE unit of the copolymerization of 30-55% weight.
Fluoroelastomer by method preparation of the present invention also comprises the cure sites that is applicable to the organo-peroxide induced cross-linking.The source of cure sites can be: but i) contain the cure site monomer of the copolymerization of bromine or iodine, ii) brominated or contain iodine chain-transfer agent or iii) i) and ii) both.The bromine or iodine atom content of introducing in the fluoroelastomer is the 0.03-1.5% of comonomer total mole number in the fluoroelastomer.Contain iodine or brominated cure site monomer and contain iodine or brominated end group (from chain-transfer agent) if fluoroelastomer comprises, then the content of iodine or bromine atoms can be the 0.03-1.5% mole of each solidified portion potential source (being cure site monomer and chain-transfer agent), altogether the iodine or the bromine cure sites of 0.06-3% mole.
The cure site monomer that contains bromine atoms can comprise other halogens, preferred fluorine.The example of brominated olefins cure site monomer has trifluoro bromine ethene; 4-bromo-3,3,4,4-tetrafluoro butene-1 (BTFB); With other materials, for example vinyl bromide, 1-bromo-2,2-difluoroethylene; The perfluor allyl bromide 98; 4-bromo-1,1,2-trifluoro butene-1; 4-bromo-1,1,3,3,4,4-hexafluoro butylene; 4-bromo-3-chloro-1,1,3,4,4-five fluorine butylene; 6-bromo-5,5,6,6-tetrafluoro hexene; 4-bromine perfluorobuttene-1 and 3,3-difluoro allyl bromide 98.Be used for ethylene bromide base ether cure site monomer of the present invention and comprise 2-bromo-perfluoroethyl perfluorovinyl base ether and CF
2Br-R
f-O-CF=CF
2(R
fBe perfluorinated alkylidene) class fluorinated compound, for example CF
2=CFOCF
2CF
2CF
2OCF
2CF
2Br; CF
2BrCF
2O-CF=CF
2And ROCF=CFBr or ROCBr=CF
2(wherein R is low alkyl group or fluoroalkyl) class fluorovinyl ether, for example CH
3OCF=CFBr or CF
3CH
2OCF=CFBr.
The suitable cure site monomer that contains the iodine atom comprises formula CHR=CH-Z-CH
2The iodate alkene of CHR-I, wherein R be-H or-CH
3Z is the optional straight or branched C that comprises one or more ether oxygen atoms
1-C
18Disclosed (entirely) fluorine polyoxy alkylidene in (entirely) fluorine alkylidene group or the United States Patent (USP) 5,674,959.Other examples of available iodinated cure site monomers have formula I (CH
2CF
2CF
2)
nOCF=CF
2And ICH
2CF
2O[CF (CF
3) CF
2O]
nCF=CF
2Deng unsaturated ethers, n=1-3 wherein, for example United States Patent (USP) 5,717, disclosed material in 036.In addition, comprise iodoethylene, 4-iodo-3,3,4,4-tetrafluoro butene-1 (ITFB); 3-chloro-4-iodo-3,4,4-trifluoro butylene; 2-iodo-1,1,2,2-tetrafluoro-1-(vinyloxy group) ethane; 2-iodo-1-(perfluoro-ethylene oxygen base)-1,1,2, the 2-tetrafluoroethylene; 1,1,2,3,3,3-hexafluoro-2-iodo-1-(perfluoro-ethylene oxygen base) propane; 2-iodine ethyl vinyl ether; 3,3,4,5,5,5-hexafluoro-4-iodine amylene; Be disclosed in United States Patent (USP) 4,694,045 with the suitable iodinated cure site monomers of trifluoro iodoethylene.Allyl group iodate thing and 2-iodo-perfluoroethyl perfluorovinyl base ether also are the available cure site monomer.
Be used for method of the present invention if contain the cure site monomer of bromine or iodine, should introduce reactor (as mentioned below) with the form of aqueous emulsion.
Owing in the process of preparation fluoroelastomer, use chain-transfer agent or the molecular weight regulator that contains the bromine or iodine atom, therefore except that cure site monomer or replace described cure site monomer, the end group that contains iodine or bromine atoms can be chosen one or two end that is present in the fluorine-containing elastomer polymer chain wantonly.Chain-transfer agent is generally formula RX
n, wherein R can be C
1-C
3Hydrocarbon, C
1-C
6Fluorohydrocarbon, C
1-C
6Chlorofluorocarbons (CFCs) or C
2-C
8Perfluoroparaffin, X are iodine or bromine, and n=1 or 2 (United States Patent (USP) 3,707,529 and 4,243,770).This reagent comprises formula CH
2X
2Material, wherein X is I or Br; X (CF
2)
nThe material of Y, wherein X is I or Br, Y is I or Br (preferred X and Y are I), and n is the integer of 3-10.
Specific examples comprises methylene iodide; 1,3-diiodo perfluo propane; 1,4-diiodo perfluo butane; 1,6-diiodo perfluo hexane; 1,8-diiodo perfluo octane; 1,10-diiodo perfluo decane; With 1-iodo-nine fluorine butane.Also can use other chain-transfer agents, for example formula RBr
nI
m(R as above defines; N and m respectively do for oneself 1 or 2) material.Preferred especially two iodinating perfluoro alkane chain-transfer agents and composition thereof.
Be used for method of the present invention if contain the chain-transfer agent of bromine or iodine, then introduce reactor with the form of aqueous emulsion.If use cure site monomer and chain-transfer agent to introduce cure sites on fluoroelastomer, then cure site monomer adds in the independent aqueous emulsion of reactor with different speed in time that can be different usually with chain-transfer agent.
The aqueous emulsion of cure site monomer or chain-transfer agent prepares by the high-shear mechanically mixing usually.In the presence of the device that produces high shear field, the optional water that comprises tensio-active agent is contacted with the organic phase that comprises cure site monomer or chain-transfer agent or their mixture.Can produce the shear field by the device (for example homogenizer or rotor/stator sets) that contains mobile or rotating part.Perhaps, can produce high shear field by the device (for example static mixer or micro-mixing machine) that does not contain mobile part substantially.Can prepare emulsion separately outside reactor, temporarily stored is transferred to polymerization reactor subsequently until needs.Perhaps can online preparation emulsion, wherein water and organic phase are added in the device that produces emulsion simultaneously, and be transferred to the reactor that does not have interim storage substantially immediately.The average droplet size of resulting aqueous emulsion is below the 50 μ m, below the preferred 20 μ m.
The optional tensio-active agent that can use is to help stable emulsion.The specific examples of suitable tensio-active agent comprise alkylsulfonate for example sodium octyl and sodium laurylsulfonate, alkyl-sulphate for example sodium lauryl sulphate and sodium decyl sulfate, alkyl carboxylate for example Sodium octoate and sodium stearate, nonionogenic tenside for example nonyl phenol poly-(oxyethane) and alkyl gather for example perfluorohexylethyl sulfonic acid, Perfluorocaprylic Acid and salt thereof, partially fluorinated sulfonic acid ten trifluoro hexyl ethylsulfonic acids and salt thereof and partially fluorinated carboxylic acid for example 3 for example of (oxyethane), perfluorinated carboxylic acid, 3,4, the sad and salt of 4-tetrahydrochysene 11 fluorine.
If there is tensio-active agent, its content is generally the 0.05-5% of water weight.The amount that is used for the tensio-active agent of emulsion depends on the specific requirement of technology and product.Usually the tensio-active agent of high level improves the stability of emulsion, but brings more impurity may for final fluoroelastomer, and these impurity can be unfavorable to the end-use performance.If dosage of surfactant is not enough, the stability of resulting emulsion can be not enough, shows droplet coalescence and form macroscopic isolating organic phase.When with the emulsion temporarily stored, for example be placed in the storage tank, and directly emulsion is added to polymerization reactor and compare, need the stability of longer emulsion.When producing isolating organic phase, lose the benefit that the present invention gives.
Can semi-batch or continuous mode carry out emulsion polymerization of the present invention.In Semi-batch Process, gaseous monomer mixture (initial monomer material) introducing that will have required composition comprises in the reactor of the aqueous solution.The described aqueous solution can be chosen wantonly and comprise surfactant emulsifiers, for example fluorochemical surfactant (ammonium perfluorocaprylate for example,
FS-62 (deriving from DuPont) or
1033D (deriving from DuPont)) or hydrocarbon tensio-active agent (for example sodium laurylsulfonate).The optional described aqueous solution also can comprise for example pH buffer reagent (phosphoric acid salt or the acetate buffer that for example are used for the pH of controlled polymerization reaction) of inorganic salt.Alkali (for example NaOH) can replace buffer reagent to be used to control pH.According to the type of fluoroelastomer to be prepared, usually pH is controlled at 1-10 (preferred 3-7).Select or in addition as another kind, in whole polyreaction, pH buffer reagent or alkali can add to reactor separately or with the form with other components (for example aqueous emulsion of polymerization starter, liquid curing site monomer or the aqueous emulsion of chain-transfer agent) combination in the different time.Also optional initial aqueous solution can comprise for example for example combination of ammonium persulphate and S-WAT of combination of ammonium persulphate (or other persulphates) or inorganic peroxide and reductive agent of water-soluble inorganic peroxide polymerization starter.
The initial monomer material comprises a certain amount of be TFE or VF
2The first monomer other monomer different with described first monomer with one or more.Setting is included in the amount of the monomer mixture in the initial material, makes that reactor pressure is 0.5-10MPa (preferred 0.5-3.5MPa).In initial gaseous state monomer material; each monomeric relative quantity depends on reaction kinetics; set the fluoroelastomer (promptly with respect to the composition of to be prepared fluoroelastomer required other monomers, very deferred reaction monomer must with high level exist) of this relative quantity to obtain having required ratio comonomer unit.
Monomer mixture is scattered in the water-bearing media, and optional also introducing at this moment of aqueous emulsion with chain-transfer agent, simultaneously reaction mixture is stirred (passing through mechanical stirring usually).If perhaps the aqueous emulsion of chain-transfer agent is used for method of the present invention, then can introduce the aqueous emulsion of chain-transfer agent at any time, added to reactor until all incremental monomer mixtures.All the chain-transfer agent of amount can once add and maybe can divide adding for several times, and the incremental monomer mixture until 100% has added to reactor.Most preferably before the beginning polymerization or after just beginning polymerization, the chain-transfer agent aqueous emulsion is introduced reactor, and the chain-transfer agent that will all measure adds to reactor when the incremental monomer mixture of gross weight 5% has added to reactor.
The temperature of semi-batch reaction mixture remains on 25 ℃-130 ℃, preferred 30 ℃-90 ℃.When the initiator thermolysis or with reductive agent reaction and resulting free radical during with dispersive monomer reaction, the beginning polymerization.
In whole polyreaction, add the gaseous monomer (being meant incremental monomer mixture material herein) of amount in addition with controlled speed, so that keep the constant reactor pressure with controlled temperature.It is roughly the same that setting is included in the required ratio of comonomer unit in the ratio of the gaseous monomer in the incremental monomer mixture material and the resulting fluoroelastomer.If method of the present invention is also used other chain-transfer agent aqueous emulsion, then described chain-transfer agent aqueous emulsion also can be chosen whenever adding in the reactor in this stage of polyreaction wantonly.Other tensio-active agent and polymerization starter also can add to reactor in this stage.The amount of the polymkeric substance that forms and the semi-invariant of incremental monomer mixture material are roughly the same.One skilled in the art will realize that, each monomeric molar ratio needn't be formed accurately identical with required comonomer unit in the resulting fluoroelastomer in the increment gaseous monomer mixture material, this is because the composition of initial material may out of true equal required final fluoroelastomer composition, perhaps, and do not participate in reaction because a part of monomer in the incremental monomer mixture material is dissolvable in water in the established polymer beads.
If but the cure site monomer of copolymerization is used for method of the present invention, cure site monomer aqueous emulsion stream is added to reactor with certain speed, make that added incremental monomer mixture reaches 99% weight when all the cure site monomer emulsion of amount has added to reactor.In this semi-batch polymerization method, the total polymerization time is generally 2-30 hour.
Continuous emulsion polymerization of the present invention is different in the following areas with Semi-batch Process.Therefore the completely filled aqueous solution in the reactor do not exist the vapour space.The solution of gaseous monomer and other components (for example aqueous emulsion of water-soluble monomer, chain-transfer agent, buffer reagent, alkali, polymerization starter, tensio-active agent etc.) is added to reactor with constant speed in independent stream.The control feed rate makes that the average polymer residence time is generally 0.2-4 hour in reactor.For reactive monomer, the residence time can lack, and for not too active monomer perfluor (alkyl vinyl) ether for example, needs the longer time.The temperature of continuous processing reaction mixture remains on 25 ℃-130 ℃, preferred 80 ℃-120 ℃.
In the method for the invention, polymerization temperature remains on 25 ℃-130 ℃.If temperature is lower than 25 ℃, then rate of polymerization is too slow, can not carry out effecting reaction with technical scale, and if temperature surpasses 130 ℃, then keep the required reactor pressure of polyreaction too high and actual infeasible.
Polymerization pressure is controlled at 0.5-10MPa, preferred 1-6.2MPa.In Semi-batch Process, begin to obtain required polymerization pressure by the amount of regulating gaseous monomer in the initial material, after the reaction beginning, regulate pressure by control increment gaseous monomer material.In continuous processing, regulate pressure by the back pressure regulator that disperses to flow out in the property management line.If it is that then the monomer concentration in the polymerization reaction system is too low, can not obtain gratifying speed of reaction because pressure is lower than 1MPa that polymerization pressure is set in the above-mentioned scope.In addition, molecular weight can not effectively increase.If pressure surpasses 10MPa, the cost of then required high-tension apparatus is very high.
The amount of the amount of the fluoroelastomer copolymer that forms and the increment material of adding is roughly the same, is 10-30 weight part multipolymer/100 weight part water-bearing medias, is preferably 20-25 weight part multipolymer/100 weight part water-bearing medias.If with the degree set that forms multipolymer in above-mentioned scope be since the amount of multipolymer less than 10 weight parts, productive rate is too low, and is undesirable, and if the amount of multipolymer surpasses 30 weight parts, then solid content is too high and stir unsatisfactorily.
In the present invention, the water-soluble peroxide that can be used for initiated polymerization for example comprises the persulfuric acid hydrogen salt of ammonium, sodium or potassium.In oxidation-reduction type causes, except superoxide, also there is for example S-WAT of reductive agent.These water-soluble peroxides can use separately or use with the form of mixtures of two or more types.The consumption of selecting is generally 0.01-0.4 weight part/100 parts by weight polymer, preferred 0.05-0.3 weight part/100 parts by weight polymer.In polymerization process, the fragment end-blocking that some fluoroelastomer polymer chain ends is produced by peroxide breakdown.
Can separate by the routine techniques that is used for the fluoroelastomer manufacturing, filter, washing and the dry fluoroelastomer emulsion for preparing gained by semi-batch or continuous processing.
Except cure sites, the preferred fluoroelastomer of the present invention comprises following copolymerization units: i) vinylidene fluoride and R 1216; Ii) vinylidene fluoride, R 1216 and tetrafluoroethylene; Iii) vinylidene fluoride, tetrafluoroethylene and perfluor (methylvinylether); Iv) tetrafluoroethylene and perfluor (methylvinylether).
Fluoroelastomer by method preparation of the present invention can adopt organo-peroxide crosslinked (i.e. sulfuration or curing).Curable fluoroelastomer composition comprises fluoroelastomer (as above definition), the b that a) prepares by method of the present invention) organo-peroxide and c) coagent.Preferred described composition also comprises for example divalent metal oxyhydroxide, bivalent metal oxide, strong basicity (being pKa＞10) organic amine Proton for example of acid acceptor
Any combination among (deriving from Aldrich) or the latter.The example of bivalent metal oxide and oxyhydroxide comprises CaO, Ca (OH)
2And MgO.
The organo-peroxide that is suitable for comprises 1, two (t-butyl peroxy)-3,5 of 1-, 5-trimethyl-cyclohexane; 1, two (t-butyl peroxy) hexanaphthenes of 1-; 2, two (t-butyl peroxy) octanes of 2-; 4, two (t-butyl peroxy) n-butyl pentanoates of 4-; 2, two (t-butyl peroxy) butane of 2-; 2,5-dimethylhexane-2,5-dihydroxyl superoxide; Di-t-butyl peroxide; The tert-butyl peroxide cumyl; Dicumyl peroxide; α, α '-two (t-butyl peroxy--sec.-propyl) benzene; 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane; 2,5-dimethyl-2,5-two (t-butyl peroxy) hexene-3; Benzoyl peroxide; T-butyl peroxy benzene; 2,5-dimethyl-2,5-two (benzoyl peroxide) hexane; The t-butyl peroxy toxilic acid; Cross the tert-butyl ester with the isobutyl carbonate propyl ester.The preferred embodiment of organo-peroxide comprises 2,5-dimethyl-2, and 5-two (t-butyl peroxy) hexane, dicumyl peroxide and α, α '-two (t-butyl peroxy--sec.-propyl) benzene.The amount that is mixed is generally the 0.05-5 weight part, is preferably 0.1-3 weight part/100 weight part fluoroelastomers.If select this concrete scope to be since the amount that superoxide exists less than 0.05 weight part, then vulcanization rate is not enough and cause that the demoulding is poor.On the other hand, if the amount that superoxide exists greater than 5 weight parts, then the compression set of cured polymer becomes too high, unacceptable.In addition, can use separately or use organo-peroxide with the array configuration of two or more types.
The coagent that is used for curable compositions is multifunctional unsaturated compound; for example triallylcyanurate, trimethylammonium acryl isocyanuric acid ester, cyanacrylate, trimethylammonium allyl group isocyanuric acid ester, triacryl formal, triallyl trimellitate, N; N '--phenylene bismaleimides, Phthalic acid, diallyl ester, tetraallyl terephthalamide, three (diallyl amine)-s-triazine, triallyl phosphite, two-alkene and N, N-diallyl acrylamide.The amount that is mixed is generally 0.1-10 weight part/100 weight part fluoroelastomers.If select this concrete concentration range to be since the amount that coagent exists less than 0.1 weight part, then the cross-linking density of cured polymer is unacceptable.On the other hand, if the amount that coagent exists surpasses 10 weight parts, then in moulding process to surperficial bloom, cause stripping feature poor.The coagent preferred range is 0.2-6 weight part/100 part fluoroelastomers.Can use separately or use unsaturated compound with the array configuration of two or more types.
In the composition that comprises the fluoroelastomer for preparing by method of the present invention, optional other components can be used as the additive that is mixed, described other components are filler for example, for example carbon black, Austinblack, graphite, thermoplastic fluoropolymer micropowder, silicon-dioxide, clay, diatomite, talcum powder, wollastonite, lime carbonate, Calucium Silicate powder, Calcium Fluoride (Fluorspan) and barium sulfate; Processing aid, for example high-grade aliphatic ester, fatty acid calcium salt, fatty amide (for example erucicamide), low molecular weight polyethylene, silicone oil, silicone grease, stearic acid, sodium stearate, calcium stearate, Magnesium Stearate, aluminum stearate and Zinic stearas; Tinting material, for example titanium white and iron oxide red.The amount of this filler is generally the 0.1-100 weight part, preferred 1-60 weight part/100 weight part fluoroelastomers.If select this scope to be because the amount that filler exists less than 0.1 weight part, does not then almost have or do not have effect, and on the other hand, if consumption greater than 100 weight parts, then can be sacrificed elasticity.The amount of the processing aid that is mixed is usually less than 10 weight parts, preferably less than 5 weight parts/100 weight part fluoroelastomers.If consumption surpasses above qualification, then influence thermotolerance unfriendly.The amount of the tinting material that is mixed is usually less than 50 weight parts, preferably less than 30 weight parts/100 weight part fluoroelastomers.If consumption greater than 50 weight parts, then stands compression set.
Usually by internal mixer or rubber mill fluoroelastomer, organo-peroxide, coagent and any other component are introduced curable composition.Can and solidify resultant composition moulding (for example molding or extrude) subsequently.Usually solidified 1-60 minute down at about 150-200 ℃.Can use the conventional rubber of the heat that provides suitable and solidification equipment to solidify press, mould, forcing machine etc.Equally,, preferably carry out after fixing operation, wherein molding or the goods extruded in baking oven (being generally about 180-275 ℃, usually in inert atmosphere) etc. the about 1-48 of reheat hour in order to make physicals and dimensional stability optimization.
Fluoroelastomer by method of the present invention preparation is used for many industrial application, comprises sealing, excellent coating, tubulation and laminate applications wind the line.
Embodiment
Testing method
According to ASTM D1646, use L (greatly) type rotor, measure mooney viscosity ML (1+10), 1 minute warm up time, 10 minutes rotor operation time down in 121 ℃ (unless otherwise indicated).
Measure limiting viscosity down in 30 ℃.For the fluoroelastomer that comprises the vinylidene fluoride copolymerization units, methylethylketone is as solvent (0.1g polymkeric substance/10ml solvent).For the fluoroelastomer that comprises tetrafluoroethylene and perfluor (methylvinylether) copolymerization units, use seven fluoro-2 of 60/40/3 volume ratio, 2, the mixed solvent of 3-three chlorobutanes, perfluor (α-butyl tetrahydrofuran) and glycol dimethyl ether (0.2g polymkeric substance/100ml solvent).
Separated the iodine content that the exsiccant polymkeric substance is measured polymkeric substance by x-ray fluorescence analysis.
Under room temperature, use Coulter LS Particle Size Analyzer, measure the emulsion droplet size 61 seconds analysis times.
Emulsion preparation
Use two kinds of different methods that prepare perfluoroalkyl diiodide aqueous emulsion in following examples.Should not think that these preparation methods make restriction to the present invention.The additive method of preparation emulsion is well known by persons skilled in the art.In method A, with flow velocity be 1ml/ minute 1,4-diiodo-Octafluorobutane and 1, the mixture of 6-diiodo-ten difluoro hexanes and flow velocity are that the perfluorohexylethyl sulfonic acid aqueous solution of 10ml/ minute 1% weight passes through SIMM-LAS trace mixing machine (IMM simultaneously, Mainz, Germany makes), form average droplet size and be 95% emulsion in 5.7 μ m and all drop less than 15 μ m.
In method B, with 22.5ml 1,4-diiodo-Octafluorobutane and 1, the mixture of 6-diiodo-ten difluoro hexanes adds to Microfluidics M-110Y trace sulfuration bed with the perfluorohexylethyl sulfonic acid aqueous solution of 427.5ml 1% weight.By trace sulfuration bed 4 times, the average droplet size that produces 5% volume is 95% emulsion less than the diiodo-compound of 0.27 μ m in 0.18 μ m and all drop with this mixture.
Embodiment 1
Add in 41 liters of reactors and comprise 17.5g perfluorohexylethyl sulfonic acid, 12.9g seven hypophosphite monohydrate disodiums and 24, the aqueous solution of 969.6g deionized water.Reactor is warming up to 80 ℃, subsequently with nitrogen purging to remove deoxidation, use the mixture of the perfluor (methylvinylether) of the tetrafluoroethylene of vinylidene fluoride, 3% weight of 43% weight and 54% weight to be forced into 1.38MPa subsequently.The solution of the ammonium persulphate of adding 30.0g 1% weight and seven hypophosphite monohydrate disodiums of 5% weight, initiated polymerization.Along with the decline of reactor pressure, add the monomer material of the perfluor (methylvinylether) of the tetrafluoroethylene of vinylidene fluoride, 10% weight of 55% weight and 35% weight, to keep-up pressure.After adding this monomer mixture of 90g, will be according to 1 of method A (above-mentioned) preparation, 4-diiodo-Octafluorobutane and 1, the emulsion of the mixture of 6-diiodo-ten difluoro hexanes in 1% (weight percent) perfluorohexylethyl sulfonic acid aqueous solution adds to reactor.After altogether 30.0g diiodide mixture adds to reactor, stop to add the diiodide mixture, add the perfluorohexylethyl sulfonic acid aqueous solution 1 minute of 1% weight again, close subsequently.Add other initiator solution as required, to keep polymerization.Totally 8, after the mixture of the perfluor (methylvinylether) of the vinylidene fluoride of 333g 55% weight, the tetrafluoroethylene of 10% weight and 35% weight adds to reactor, reaction is stopped, reactor is reduced pressure.Make 33,525g 23.76% weight solid latex.By in latex, adding the Tai-Ace S 150 isolating polymer, dry down in 70 ℃ subsequently.
Embodiment 2
Add in 41 liters of reactors and comprise 17.5g perfluorohexylethyl sulfonic acid, 12.9g seven hypophosphite monohydrate disodiums and 24, the aqueous solution of 969.6g deionized water.Reactor is warming up to 80 ℃, subsequently with nitrogen purging to remove deoxidation, use the mixture of the perfluor (methylvinylether) of the tetrafluoroethylene of vinylidene fluoride, 3% weight of 43% weight and 54% weight to be forced into 1.38MPa subsequently.The solution of the ammonium persulphate of adding 30.0g 1% weight and seven hypophosphite monohydrate disodiums of 5% weight, initiated polymerization.Along with the decline of reactor pressure, add the monomer material of the perfluor (methylvinylether) of the tetrafluoroethylene of vinylidene fluoride, 10% weight of 55% weight and 35% weight, to keep-up pressure.After adding this monomer mixture of 90g, subsequently will be according to 1 of method A (above-mentioned) preparation, 4-diiodo-Octafluorobutane and 1, the emulsion of the mixture of 6-diiodo-ten difluoro hexanes in 1% (weight percent) perfluorohexylethyl sulfonic acid aqueous solution adds to reactor.After altogether 10.0g diiodide mixture has added to reactor, stop to add the diiodide mixture, add the aqueous solution 1 minute of the perfluorohexylethyl sulfonic acid of 1% weight again, close subsequently.After adding the 833g monomer mixture, will be equally according to 1 of method A (above-mentioned) preparation, 4-diiodo-Octafluorobutane and 1, the emulsion of the mixture of 6-diiodo-ten difluoro hexanes in 1% (weight percent) perfluorohexylethyl sulfonic acid aqueous solution adds to reactor.After other 20.0g diiodide mixture has added to reactor, stop to add the diiodide mixture, add the aqueous solution 1 minute of the perfluorohexylethyl sulfonic acid of 1% weight again, close subsequently.Add other initiator solution as required, to keep polymerization.Totally 8, after the mixture of the perfluor (methylvinylether) of the vinylidene fluoride of 333g 55% weight, the tetrafluoroethylene of 10% weight and 35% weight has added to reactor, reaction is stopped, reactor is reduced pressure.Make 33,800g 25.39% weight solid latex.By in latex, adding the Tai-Ace S 150 isolating polymer, dry down in 70 ℃ subsequently.
Comparing embodiment 1
Add in 41 liters of reactors and comprise 17.5g perfluorohexylethyl sulfonic acid, 12.9g seven hypophosphite monohydrate disodiums and 24, the aqueous solution of 969.6g deionized water.Reactor is warming up to 80 ℃, to remove deoxidation, uses the mixture of the perfluor (methylvinylether) of the tetrafluoroethylene of vinylidene fluoride, 3% weight of 43% weight and 54% weight to be forced into 1.38MPa subsequently with nitrogen purging.The solution of the ammonium persulphate of adding 30.0g 1% weight and seven hypophosphite monohydrate disodiums of 5% weight, initiated polymerization.Along with the decline of reactor pressure, add the monomer material of the perfluor (methylvinylether) of the tetrafluoroethylene of vinylidene fluoride, 10% weight of 55% weight and 35% weight, to keep-up pressure.After adding this monomer mixture of 90g, in 10 minutes, in reactor, directly add 30.0g 1 altogether, 4-diiodo-Octafluorobutane and 1, the mixture of 6-diiodo-ten difluoro hexanes.Add other initiator solution as required, to keep polymerization.Totally 8, after the mixture of the perfluor (methylvinylether) of the vinylidene fluoride of 333g 55% weight, the tetrafluoroethylene of 10% weight and 35% weight has added to reaction, reaction is stopped, reactor is reduced pressure.Make 33,695g 25.31% weight solid latex.By in latex, adding the Tai-Ace S 150 isolating polymer, dry down in 70 ℃ subsequently.
The analytical results of these embodiment is shown in Table I.These embodiment use 30.0g 1 separately, 4-diiodo-Octafluorobutane and 1, the mixture of 6-diiodo-ten difluoro hexanes.The iodine content of this mixture is 48.6% weight.Therefore, each embodiment polymkeric substance obtains 14.58g iodine.
Table I
| Embodiment | 1 | 2 | Comparing embodiment 1 |
| Polymkeric substance, g | 7965 | 8602 | 8528 |
| Limiting viscosity | 0.71 | 0.72 | 0.94 |
| Mooney viscosity | 41.2 | 43.1 | 79.3 |
| Iodine, the % mole | 0.12 | 0.12 | 0.09 |
| Iodine, % weight | 0.182 | 0.177 | 0.140 |
| Iodine in the polymkeric substance, g | 14.50 | 15.22 | 11.93 |
| The iodine yield, % | 99 | 104 1 | 82 |
1Experimental error 100%
Data in the Table I show, use perfluoroalkyl diiodide emulsion to make this increase of iodo 100% of introducing in the polymkeric substance, and compare with the comparing embodiment that is prepared by pure perfluoroalkyl diiodide, resulting polymkeric substance has lower limiting viscosity and mooney viscosity.
Embodiment 3
Add in 41 liters of reactors and comprise 17.5g perfluorohexylethyl sulfonic acid, 12.9g seven hypophosphite monohydrate disodiums and 24, the aqueous solution of 969.6g deionized water.Reactor is warming up to 80 ℃, to remove deoxidation, uses the mixture of the perfluor (methylvinylether) of the tetrafluoroethylene of vinylidene fluoride, 3% weight of 43% weight and 54% weight to be forced into 1.38MPa subsequently with nitrogen purging.The solution of the ammonium persulphate of adding 30.0g 1% weight and seven hypophosphite monohydrate disodiums of 5% weight, initiated polymerization.Along with the decline of reactor pressure, add the monomer material of the perfluor (methylvinylether) of the tetrafluoroethylene of vinylidene fluoride, 10% weight of 55% weight and 35% weight, to keep-up pressure.After adding this mixture of 90g, with 25ml/ minute speed add 5% volume as 1 of preparation as described in the method B (above-mentioned), 4-diiodo-Octafluorobutane and 1, the emulsion of the mixture of 6-diiodo-ten difluoro hexanes in the perfluorohexylethyl sulfonic acid solution of 1% weight.Stop to feed in raw material after 10 minutes.Add other initiator solution as required, to keep polymerization.Totally 8, after the mixture of the perfluor (methylvinylether) of the vinylidene fluoride of 333g 55% weight, the tetrafluoroethylene of 10% weight and 35% weight adds to reaction, reaction is stopped, reactor is reduced pressure.Make 24.95% weight solid latex.By in latex, adding the Tai-Ace S 150 isolating polymer, dry down in 70 ℃ subsequently.The mooney viscosity of this polymkeric substance is 42, and limiting viscosity is 0.72.
Embodiment 4
Add in 41 liters of reactors and comprise 34.5g perfluorohexylethyl sulfonic acid, 40.0g seven hypophosphite monohydrate disodiums and 24, the aqueous solution of 925.5g deionized water.Reactor is warming up to 80 ℃, to remove deoxidation, uses the mixture of the perfluor (methylvinylether) of the tetrafluoroethylene of 25% weight and 75% weight to be forced into 2.00MPa subsequently with nitrogen purging.The solution of the ammonium persulphate of adding 40.0g 1% weight and seven hypophosphite monohydrate disodiums of 5% weight, initiated polymerization.Along with the decline of reactor pressure, add the monomer material of the perfluor (methylvinylether) of the tetrafluoroethylene of 52% weight and 48% weight, to keep-up pressure.After having added this mixture of 45g, with 16.5ml/ minute speed add 9% volume as 1 of preparation as described in the method A (above-mentioned), 4-diiodo-Octafluorobutane and 1, the emulsion of the mixture of 6-diiodo-ten difluoro hexanes in the perfluorohexylethyl sulfonic acid solution of 1% weight.Stop to feed in raw material after 7 minutes.Add other initiator solution as required, to keep polymerization.Totally 8, after the mixture of the perfluor (methylvinylether) of the tetrafluoroethylene of 333g 52% weight and 48% weight adds to reaction, reaction is stopped, reactor is reduced pressure.Make 24.03% weight solid latex.By in latex, adding the Tai-Ace S 150 isolating polymer, dry down in 70 ℃ subsequently.The mooney viscosity of this polymkeric substance is 69.5.
Embodiment 5
Add in 41 liters of reactors and comprise 24.7g perfluorohexylethyl sulfonic acid, 20.0g seven hypophosphite monohydrate disodiums and 24, the aqueous solution of 955.3g deionized water.Reactor is warming up to 80 ℃, to remove deoxidation, uses the mixture of the R 1216 of the tetrafluoroethylene of vinylidene fluoride, 2% weight of 25% weight and 73% weight to be forced into 1.72MPa subsequently with nitrogen purging.The solution of the ammonium persulphate of adding 50.0g1% weight and seven hypophosphite monohydrate disodiums of 5% weight, initiated polymerization.Along with the decline of reactor pressure, add the vinylidene fluoride of 50% weight, the monomer material of the R 1216 of the tetrafluoroethylene of 20% weight and 30% weight is to keep-up pressure.After adding this mixture of 45g, with 16.5ml/ minute speed add 9% volume as 1 of preparation as described in the method A (above-mentioned), 4-diiodo-Octafluorobutane and 1, the emulsion of the mixture of 6-diiodo-ten difluoro hexanes in the perfluorohexylethyl sulfonic acid solution of 1% weight.12.5 stop after minute feeding in raw material.Add other initiator solution as required, to keep polymerization.Totally 8, the vinylidene fluoride of 333g 50% weight after the mixture of the R 1216 of the tetrafluoroethylene of 20% weight and 30% weight adds to reaction, stops reaction, and reactor is reduced pressure.Make 25.46% weight solid latex.By in latex, adding the Tai-Ace S 150 isolating polymer, dry down in 70 ℃ subsequently.The mooney viscosity of this polymkeric substance is 21, and limiting viscosity is 0.55.
Claims (9)
- One kind prepare have bromine, the method for the fluoroelastomer of iodine or bromine and iodine cure sites, described method comprises:(A) in reactor, add a certain amount of aqueous solution;(B) add a certain amount of initial monomeric mixture to form reaction medium in described reactor, described initial monomeric mixture comprises: i) first monomer, and described first monomer is selected from vinylidene fluoride and tetrafluoroethylene; But the ii) monomer of one or more other copolymerization different with described first monomer, wherein said other monomer is selected from Fluorine containing olefine, fluorine-containing ether, propylene, ethene and composition thereof;(C) add at least a aqueous emulsion that comprises the solidified portion potential source in described reactor, described solidified portion potential source is selected from: i) contain the iodine cure site monomer, ii) brominated cure site monomer, iii) contain iodine chain-transfer agent and iv) brominated chain-transfer agent; The average droplet size of wherein said emulsion is below the 50 μ m; With(D) the described monomer of polymerization in the presence of radical initiator has the fluoroelastomer of cure sites with formation.
- 2. the process of claim 1 wherein step C) in described aqueous emulsion to comprise average droplet size be the following solidified portion potential sources of 20 μ m.
- 3. the process of claim 1 wherein step C) in described aqueous emulsion also comprises surfactant.
- 4. the method for claim 3, wherein said tensio-active agent is selected from sodium octyl, sodium laurylsulfonate, sodium lauryl sulphate, sodium decyl sulfate, Sodium octoate, sodium stearate, nonyl phenol poly-(oxyethane), perfluorohexylethyl sulfonic acid and salt, Perfluorocaprylic Acid and salt thereof, ten trifluoro hexyl ethylsulfonic acids and salt and 3,3,4, the sad and salt of 4-tetrahydrochysene 11 fluorine.
- 5. the method for claim 3, wherein step C) in described aqueous emulsion by high-shear mechanically mixing water, solidified portion potential source and tensio-active agent preparation.
- 6. the process of claim 1 wherein that described fluoroelastomer comprises copolymerization units and cure sites, described copolymerization units is selected from i) vinylidene fluoride and R 1216; Ii) vinylidene fluoride, R 1216 and tetrafluoroethylene; Iii) vinylidene fluoride, tetrafluoroethylene and perfluor (methylvinylether); Iv) tetrafluoroethylene and perfluor (methylvinylether); Described cure sites is selected from bromine atoms, iodine atom and iodine and bromine atoms.
- 7. the process of claim 1 wherein that described solidified portion potential source is to be selected from following brominated cure site monomer: trifluoro bromine ethene; 4-bromo-3,3,4,4-tetrafluoro butene-1; Vinyl bromide; 1-bromo-2, the 2-difluoroethylene; The perfluor allyl bromide 98; 4-bromo-1,1,2-trifluoro butene-1; 4-bromo-1,1,3,3,4,4-hexafluoro butylene; 4-bromo-3-chloro-1,1,3,4,4-five fluorine butylene; 6-bromo-5,5,6,6-tetrafluoro hexene; 4-bromine perfluorobuttene-1; 3,3-difluoro allyl bromide 98; 2-bromo-perfluoroethyl perfluorovinyl base ether; CF 2=CFOCF 2CF 2CF 2OCF 2CF 2Br; CH 3OCF=CFBr and CF 3CH 2OCF=CFBr.
- 8. the process of claim 1 wherein that described solidified portion potential source is to be selected from the following iodine cure site monomer that contains: iodoethylene; 4-iodo-3,3,4,4-tetrafluoro butene-1; 3-chloro-4-iodo-3,4,4-trifluoro butylene; 2-iodo-1,1,2,2-tetrafluoro-1-(vinyloxy group) ethane; 2-iodo-1-(perfluoro-ethylene oxygen base)-1,1,2, the 2-tetrafluoroethylene; 1,1,2,3,3,3-hexafluoro-2-iodo-1-(perfluoro-ethylene oxygen base) propane; 2-iodine ethyl vinyl ether; 3,3,4,5,5,5-hexafluoro-4-iodine amylene; The trifluoro iodoethylene; Allyl iodide; With 2-iodo-perfluoroethyl perfluorovinyl base ether.
- 9. the process of claim 1 wherein that described solidified portion potential source is to be selected from the following iodine chain-transfer agent that contains: i) CH 2X 2, wherein X is I or Br; Ii) X (CF 2) nY, wherein X is I or Br, Y is I or Br, and n is the integer of 3-10; Iii) X (CF 2) nY, wherein X and Y are I, and n is the integer of 3-10.
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| US73138105P | 2005-10-28 | 2005-10-28 | |
| US60/731,381 | 2005-10-28 | ||
| US11/529,035 | 2006-09-28 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102216345A (en) * | 2008-11-13 | 2011-10-12 | 纳幕尔杜邦公司 | Fluorosulfonates |
| CN104893189A (en) * | 2015-05-25 | 2015-09-09 | 巨化集团技术中心 | Preparation method of enhanced polyvinylidene fluoride resin |
| CN106832256A (en) * | 2017-01-18 | 2017-06-13 | 济南齐氟新材料技术有限公司 | A kind of preparation method of fluorine-containing nonionic surfactant |
| CN110446723A (en) * | 2017-03-31 | 2019-11-12 | 大金工业株式会社 | The use of surfactant and surfactant of fluoropolymer-containing manufacturing method, polymerization |
-
2006
- 2006-10-27 CN CNA2006800402959A patent/CN101296954A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102216345A (en) * | 2008-11-13 | 2011-10-12 | 纳幕尔杜邦公司 | Fluorosulfonates |
| CN102216345B (en) * | 2008-11-13 | 2013-12-18 | 纳幕尔杜邦公司 | Fluorosulfonates |
| CN104893189A (en) * | 2015-05-25 | 2015-09-09 | 巨化集团技术中心 | Preparation method of enhanced polyvinylidene fluoride resin |
| CN106832256A (en) * | 2017-01-18 | 2017-06-13 | 济南齐氟新材料技术有限公司 | A kind of preparation method of fluorine-containing nonionic surfactant |
| CN106832256B (en) * | 2017-01-18 | 2020-07-28 | 济南齐氟新材料技术有限公司 | Preparation method of fluorine-containing nonionic surfactant |
| CN110446723A (en) * | 2017-03-31 | 2019-11-12 | 大金工业株式会社 | The use of surfactant and surfactant of fluoropolymer-containing manufacturing method, polymerization |
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